Mordanting



Patented Apr. 21, 1953 MORDANTING Otis Willard Murray, Burbank, Calif., assignor to E. I. du. Pont de Nemours & Company, Wi1- mington, Del., a corporation of Delaware No Drawing. Application August 7, 1947, Serial No. 767,343

Claims.

This invention relates to improvements in the art of mordanting and, more particularly, to mordanting layers in photographic elements. Still more particularly it relates to processes of reproducing photographic color imagesand to elements therefor which utilize novel organic mor dants. Still more particularly it relates to such processes and elements wherein bis-(alphanaphthol carbonamide) hydrocarbons and hydrocarbon ethers are utilized as mordants in the formation of color images.

An object of this invention is to improve the art of mordanting. Another object is to provide improvements in the mordanting of photographic layers. A further object is to provide an improvedmethod of aifixing basic dyes in photographic layers by mordanting. procedures. A more specific object is to provide improvements in the formation of relief images by the use of mordants for fixin basic dyes to colloid layers. Still other objects will be apparent from the following description of the invention.

It has been found that the 1- and 2-hydroxynaphthoic acid amides of the general formula where X is hydrogen, alower aliphatic carboxylic acid acyl radical (RfCO) where R is an alkyl radical of 1 to 4 carbon atoms or a carbalkoxy group of 2 to 5 carbon atoms and His the radical of an aromatic amine, have a marked mordant-x' ing action of water-permeable colloid materials especially proteins, e. g., gelatin, casein and albumin, and fix basic dyes thereto. Thus the land Z-hydroxy-naphthoic acid amides and their 1- and 2-acyl derivatives of various primary aromatic monoand di-amides, -e. g., aniline, naphthylamine, benzidine and their homologues, 4,4- diaminostilbene and its homologues, 4,4-di aminoazoxybenzene and its homologues, di-

aminoarylureas, di(aminobenzoyl, 4,4 amino-'- phenyDurea, aminobenzthiazoles, dihydrothiotolidine, aminoazophenanthrenes, 3,6-diaminocarbazole, etc. g Y

In the preferred aspect of the invention naphthol carbonamides of the general formula whereina position ortho or para to the hydroxyl- (Cl. Mil-149.1)

groups in the naphthalene nucleus is reactive and A is the divalent radical of an organic diamine of at least eight carbon atoms and contains at least one benzene nucleus and X is hydrogen, lower aliphatic acyl (RCO where R is an alkyl radical 'of '1 to 4 carbon atoms), and

carbalkoxy groups of l to 5 carbon atoms are used. They have a strong mordanting action on fibrous and water-permeable colloid materials especially protein materials, e. g., gelatin, and fix basic dyes thereto.

The radical A with the imino groups constitutes the residue of various organic aromatic diamines, e. g., 1,5-diaminonaphthalene,, 2,2'-, 2,4-, and 4,4fqdiaminostilbenes, p-diaminodie phenyl ether, benzidine l,4- bis-,(aminoethyl) benzene, lA-bis-(beta-aminoethyl)benzene, etc. and their homologues. of such amines and residues may contain various innocuous radicals or groups which do not enter into dye coupling reactions with diazo compounds or color coupling developing agents. nocuous radicals include hydrocarbon radicals,

alkoxy groups, nitro groups, halogen atoms, e. g.,

chlorine and bromine, acid groups."

Reactive positions ortho or para to the hysulfonic, and carboxylic droxyl groups of the naphthalene nuclei in'the'.

preferred naphtholcarbonamides include hydro'-' gen atoms and replaceablegroups, e. g., chlorine or bromine atoms, and sulfonic 'or' carboxylic acid groups.

especially the chloride with an organic primary diamine of the above type. Two mols of the acid halide should be present for each mol of di-" amine to facilitate the acylation reaction. The reaction is preferably carried out in the pres'- sponding sulfonic acid chloride in the reactions described in United States Patent 2,395,484.

Still more preferred mordants have the formula The hydrocarbon nuclei Such in- The carbonamides can be made by reacting an alpha-hydroxynaphthoic acid halide wherein X has the above significance, it being understood that the various nuclei may contain substituents as above described and the para positions to the OX groups are reactive, e. g., unsubstituted or contain a readily replaceable group. These compounds can be prepared by reacting alpha-oxynaphthoic acid chloride with appropriate amines in the presence of suitable condensing agents, e. g., pyridine.

The invention in its broadest aspects comprises treating a material with a naphthol carbonamide mordanting agent of the above type and applying a basic dye to the mordanted material. Such suitable materials includ filaments, fibers, films, and foils composed of wool, silk, nylon, casein, gelatin, etc. The dyed material has excellent stability to light and washing.

It has been further discovered that these organic mordants are especially useful for fixing dyes in water-permeable colloid layers of photographic elements including hydrophilic hydroxyl polymers, protein, and cellulose derivative layers in the formation of relief images and in a pigmented colloid film or layer in which the said water-permeable colloid layer contains both the novel mordant and a suitable basic dye.

Basic dyes mordanted by the novel naphthol carbonamides described above evidence no change in color and the brilliancy of the original dyes is preserved throughout processing. Basic dyes, in general, are suitable in the process including Rhodamine 5G C. I. No. 746 Acridine Orange NO C. I. No. 788 Auramine C. I. No. 655 Basic Brown BR C. I. No. 332 Basic Navy Blue D Conc C. I. No. 909 Rhoduline Blue 6G C. I. No. 658 Brilliant Green B Crystals C. I. No. 662 Victoria Blue B C. I. No. 729 Fuchsine C. I. No. 677 Methylene Blue BX C. I. No. 922 Phosphine G C. I. No. 793

Novel pigmented layers includin carbon tissues can be advantageously prepared by admixing one of the aforedescribed mordants with water-permeable colloids, e. g., gelatin, albumin, casein, polyvinyl alcohol, etc., dispersed in aqueous solution until a uniform colloidal dispersion is obtained. The selected basic dyestuff is then added to the dispersion preferably from an aqueous solution. The solution is then chilled, set, extruded into noodles which are washed until no dye bleeds out. At this stage the mordanting agent is holding or fixing the maximum amount of basic dye. The colloidal composition is then liquefied and coated onto a support, e. g.. a thin paper sheet, and dried. The mordanted colloid layers are then used for printing from color separation negatives in the same manner that the prior art carbon tissues are used. Three gelatin relief images containing insoluble pigments obtained from mordanting basic dyes by means of the novel agents of this invention and corresponding in color to three-color separation negatives thus may be superposed in register on a support.

The invention will be further illustrated but is not intended to be limited by the following examples.

EXAMPLE I To one kilogram of a gelatino-silver iodobromide emulsion containing two grams of Rhodamine B (C. I. No. 749) was added 50 cc.

of 10% 4,4 bis (1- naphthol 2- carbonamidophenyl) ether prepared by substituting 4.5 parts of l-naphthol-2-carboxylic acid chloride for the sulfonyl chloride of Example I of United States Patent 2,395,484 in water containing one gram of sodium hydroxide. Th mixture was adjusted to pH 7.5 with dilute hydrochloric acid and applied to a transparent, cellulose acetate support. The element was exposed through the base from a green color separation negative and then treated in the following manner:

(1) Develop for five minutes in a solution made by admixing the Solutions A and B which follow:

Solution A Grams Sodium sulfite 3.25

Pyrogallol 14.15

Potassium bromide 3.25 Water to 1.00 liter.

Solution B Grams Sodium carbonate 56.60

Water to 1.00 liter.

(2) Wash five minutes, then bathe in warm water F.) whereupon a relief image in color is formed. The silver may be removed, if desired, by means of a ferricyanide bleach, e. g., a slightly alkaline solution of 5% potassium ferricyanide, followed by fixing in plain hypo.

Similar elements can be made by substituting other basic dyes which form the proper colored images for color separation records. The elements can be printed from other appropriate color separation negatives in like manner. The final dye component image records can then be superimposed in register or transferred to a permanent support. Multicolored pictures of a fine gradation and uniformity superior to that obtainable with ordinary gelatin matrices are formed.

EXAMPLE II A gelatin dispersion was made by admixing the following two solutions:

Solution A Gelatin "grams" 10.0 Water cc 150.0

Solution B CzHsOH cc 20.0 4,4-bis(1-naphthol 2 carbonamido-phenyl)ether grams 2.0 NaOH (5 N.) cc 2.0 Water cc 10.0

The solution was adjusted to a pH 8 by the addition of acetic acid. Two grams of Rhodamine 5G (C. I. No. 746) were then added with stirring. After a uniform dispersion was obtained, the solution was chilled, set, and extruded through a die into noodles which were washed until dye no longer was removed. The noodles were melted and coated onto photographic paper. The resulting layers can be made in any desired shade or color by substitution of the appropriate basic dye. The resulting layers are then sensitized with potassium dichromate, squeegeed into contact with positive prints from color separation negatives. The pigmented layers are then stripped, laid face down on clean plastic sheets and squeegeed into firm contact. After standing for a few minutes, the combinations are immersed in warm water. The unhardened gelatin becomes softened and the paper may be stripped away.

erries.

Further washing in warm water removes excess unharde'nedpigmented gelatin and leavescolored relief images. The images maybe transferred to new supports in register.

EXAMPLE III Elements useful in the formation of transfer prints by imbibition can be made by coating a suitable transparent support or an opaque paper support with a gelatin solution containing a naphthol carbonamide mordanting agent of the above type, but devoid of dye, after the manner described in Example II. The layer can then be hardened by treatment in a solution of the composition:

Potassium dichromate grams Water liter 1 After drying, the film is heated to 120 F. for several hours. A sharp image in the form of a basic dye may then be imbibed-in the hardened gelatin surface of the element by contact with a matrix carrying a relief image from a color separation negative, said image being obtained by staining a gelatin relief in a solution containing an appropriate basic dye.

EXAMPLEIV A gelatin dispersion was made by admixing the following two solutions:

Solution A Gelatin grams 16.0 Water cc 100,0

Solution B 1-hydroxy-2-p-chloranilide grams 1.5 Sodium hydroxide (20%) cc 1.5

EXAMPLE V A solution of 2,3-hydroxynaphthoic acid anilide gram 1.0 Ethanol cc 10.0 NaO'H (20%) cc 1.0

was made and the pH was adjusted to 7.5 with 2% I-ICl. A solution of 100 grams of 10% gelatin was divided into equal parts and 0.25 grams of Rhodamine B (C. I. 749) was added to each. The solution of 2,3 -hydroxynaphthoic acid anilide was added to one divided part of gelatin solution. After setting, the dyed gels were noodled and washed. The dye washed from the control more rapidly than the test containing the mordant.

The invention obviously is not limited to the particular procedures described in the above examples but, on the contrary, can be used in various other processes of producing photographic images which include the step of mordanting dyes.

An advantage of the invention resides in the superior fixing action of the mordants with respect to basic dyes. Methylene Blue (C. I. No. 922), Rhodamine B (C. I. No. 749), and Auramine (C. I. No. 655), for example, will not satisfactorily anchor to gelatin.- Howeven-when the present mordants are used they become fastly fixed in gelatin layers.

The novel naphtholcarbonamides described above, as previously stated, can be used to mordant or aifix basic dyes to other materials. Thus, they can be used in the same manner as other mordants in mordanting wool, silk, nylon, casein, etc., filaments, fibers, films, and foils, by bathing, impregnating, or precipitating on such materials the novel sulfonamides. A practical method of treating wool comprises bathing wool yarn or fibers in an aqueous alkaline solution containing one to five per cent of the carbonamides, then neutralizing the impregnated fiber with acid. The other materials just mentioned can be treated in an analogous manner. When basic dyes are applied to the so mordanted material, the resulting dyed material is fastly dyed and has good stability to light and washing.

A remarkable improvement for increase in with the unmordantdyed material results from dyeing in accordance with this invention. Basic dyes as a class are notoriously fugitive to light, a circumstance which seriously restricts their applicability. The increased stability above referred to is quite surprising and unexpected. The novel mordants have the advantage that they admit of the use of basic dyes which are not suitable in many dyeing operations because of their fugitive character.

As many widely different embodiments of this invention can be made without departing from the spirit and scope thereof, it is to be understood that the invention is not to be limited except as defined by the claims.

What is claimed is:

1. A process which comprises treating a waterpermeable colloid with an aqueous alkaline solution of a naphthol carbonamide of the general formula:

OX OX wherein one of the positions ortho and para to the OX substituent is reactive, A is the divalent radical of an organic diamine of at least eight carbon atoms which contains at least one benzene nucleus and X is a member taken from the group consisting of hydrogen, aliphatic acyl radicals of 1 to 5 carbon atoms and carbalkoxy radicals of 1 to 5 carbon atoms, and applying an aqueous solution of a basic dye to the treated material.

2. A process which comprises treating a water permeable protein with an aqueous alkaline solution of a naphthol carbonamide of the general formula:

OX OX wherein A is the divalent radical of an organic diamine of at least eight carbon atoms which contains at least one benzene nucleus and X is a member taken from the group consisting of hydrogen, aliphatic acyl radicals of 1 to 5 carbon atoms and carbalkoxy radicals of 1 to 5 carbon wherein one of the positions ortho and para to the OX substituent is reactive, A is the divalent radical of an organic diamine of at least eight carbon atoms which contains at least one benzene nucleus and X is a member taken from the group consisting of hydrogen, aliphatic acyl radicals of 1 to 5 carbon atoms and carbalkoxy radicals of 1 to 5 carbon atoms, hardening the coated layer by treating it with an aqueous solution of potassium dichromate, staining a gelatin relief image with an aqueous solution contain- 8 ing a basic dye and pressing the relief image into contact with the coated layer on said support whereby an image of said such basic dye is imbibed by the coated layer and is mordanted by said naphthol carbonamide.

4. A process as set forth in claim 2 wherein the naphthol carbonamide is 4,4'-bis-(1naphthol-2- carbonamiclophenyl) ether.

5. A process as set forth in claim 3 wherein said naphthol carbonamide is 4,4-bis-(1-naphthol-Z-carbonamidophenyl) ether.

OTIS WILLARD MURRAY.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 1,562,828 Hernandez-Mejia Nov. 24, 1925 1,899,856 Montmollin Feb. 28, 1933 2,054,261 Lierg Sept. 15, 1936 2,124,371 Gschopf et al July 19, 1938 2,156,821 Schneider May 2, 1939 2,179,239 Wellmanns et a1. Nov. 7, 1939 

2. A PROCESS WHICH COMPRISES TREATING A WATER PERMEABLE PROTEIN WITH AN AQUEOUS ALKALINE SOLUTION OF A NAPHTHOL CARBONAMIDE OF THE GENERAL FORMULA: 